CN103730657B - A kind of preparation method of lithium phosphate/carbon-coated lithium iron phosphate composite - Google Patents
A kind of preparation method of lithium phosphate/carbon-coated lithium iron phosphate composite Download PDFInfo
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- CN103730657B CN103730657B CN201410010622.2A CN201410010622A CN103730657B CN 103730657 B CN103730657 B CN 103730657B CN 201410010622 A CN201410010622 A CN 201410010622A CN 103730657 B CN103730657 B CN 103730657B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 60
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 238000013467 fragmentation Methods 0.000 claims description 16
- 238000006062 fragmentation reaction Methods 0.000 claims description 16
- 239000004576 sand Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940071264 lithium citrate Drugs 0.000 claims description 4
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000004033 diameter control Methods 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229940001468 citrate Drugs 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000010416 ion conductor Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 P elements mol ratio Chemical compound 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910010695 LiFeP2O7 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of high-performance lithium phosphate/carbon-coated lithium iron phosphate composite, mainly comprise the not preparation of the LiFePO4 of carbon coated and the preparation process of lithium phosphate/carbon-coated lithium iron phosphate composite. This method is prepared the not LiFePO4 of carbon coated by first sintering, next in two sneak out journey, adds a certain amount of lithium phosphate, carbon source, finally prepares and has the coated composite ferric lithium phosphate material of lithium phosphate/carbon. Lithium phosphate is a kind of fast-ionic conductor, reaches on the one hand the object that improves LiFePO4 electrical conductivity, reaches on the other hand the object that improves LiFePO4 overall performance.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, particularly relate to the coated phosphoric acid of a kind of high-performance lithium phosphate/carbonThe preparation method of iron lithium composite material.
Background technology
Lithium ion battery, since 1991 come out, has received people's vast concern always. And as lithium ion battery importantThe positive electrode of part, also becomes the research emphasis of material gradually. At present, positive electrode research mainly concentrates on containing lithiumTransition metal oxide, as the LiC of six side's layer structuresOO2、LiMnO2LiMn with spinel structure2O4And polynary transitionMetal oxide LiNi1-x-yCOxMnyO2Deng.
Due to ferro element rich content and environmental friendliness in the earth's crust, in recent years, people have more and more studied the lithium of iron contentSalt, to replace current positive electrode. Especially the LiFePO of people's reported first olivine structural such as Goodenough in 19974Since thering is the characteristic of reversible de-, embedding lithium, LiFePO4Become gradually one of focus of anode material for lithium-ion batteries research. At present,About synthetic LiFePO4The method of positive electrode has a lot of reports, but at the main or high temperature solid-state method of industrial realization, butLiFePO4Lower electrical conductivity (10-9And lithium ion diffusion coefficient (1.8 × 10 S/cm)-14cm2/ s) these intrinsic shortcomings, causeLiFePO prepared by conventional method4Chemical property is not good, particle diameter skewness, hindered its industrialized development. ForSolve LiFePO4The problem that electrical conductivity is low, lithium ion diffusion coefficient is slow. In order to improve the performance of material, researcher does both at home and abroadA large amount of related works, mainly by carbon be coated, ion doping, particle nanometer, inorganic lithium salt method for coating etc.
About the coated aspect of inorganic lithium salt, people mainly lay particular emphasis in LFP surface in situ solid phase and generate pyrophosphate and some phosphoric acidThe fast-ionic conductor of salt. The formation of these fast-ionic conductors, can improve LiFePO4The electric transmission situation at interface, improves LiFePO4Electrical conductivity and corresponding chemical property. As adopting two-step method, China Patent Publication No. CN102244241A prepares pyrophosphoric acid lithiumCoated composite ferric lithium phosphate material. Prepare the not LiFePO4 of carbon coated by once sintered, and in ensuing batch mixing mistakeIn journey, add lithium source, phosphorus source and carbon source, generate ferric pyrophosphate lithium through double sintering at LiFePO4 surface in situ. As special in ChinaProfit publication number CN120842713A is disposable mixes source of iron, phosphorus source, lithium source, vanadium source, aluminium source and carbon source, through burningKnot is prepared has LiFeP2O7、LiAlP2O7And Li3V2(PO4)3The LiFePO4 of these Phosphate coatings. First method preparationThe coated lithium phosphate particle of pyrophosphoric acid lithium controlled, but also there is certain shortcoming, the He Lin source, lithium source adding is in double sintering mistakeJourney solid phase reaction may not all generate pyrophosphoric acid lithium, likely also can generate the miscellaneous of other, and this likely can have influence on carbon sourceBe uniformly distributed and the chemical property of LiFePO4. And the coated phosphoric acid of phosphoric acid lithium salts that second method is used one-step method to prepareIron lithium, exists that material granule particle diameter is uncontrollable, coated inhomogeneous, the shortcoming such as material uniformity is poor of carbon.
Summary of the invention
The present invention is intended to prepare high performance lithium phosphate/carbon-coated lithium iron phosphate composite. Prepare not by first sinteringThe LiFePO4 of carbon coated, and in batch mixing, add certain lithium phosphate and carbon source for the second time, through double sintering, finally preparationGo out to have lithium phosphate/carbon-coated lithium iron phosphate composite, reach on the one hand the object that improves LiFePO4 electrical conductivity, on the other handReach the object that improves LiFePO4 overall performance.
The preparation of lithium phosphate/carbon-coated lithium iron phosphate composite, mainly comprises not preparation and the phosphoric acid of the LiFePO4 of carbon coatedThe preparation process of lithium/carbon-coated lithium iron phosphate composite. Technical scheme of the present invention is as follows:
A preparation method for lithium phosphate/carbon-coated lithium iron phosphate composite, comprises the following steps:
1) lithium source, source of iron, phosphorus source are pressed to element mol ratio for (1～1.2): (0.9～1.2): (0.9～1.2), at organic solvent orIn deionized water, carry out batch mixing for the first time, phosphorus source, lithium source, source of iron are joined in blue-type mulling machine sequentially, grind 2～3After hour, the slurry grinding out is poured in sand mill and is ground;
2) will grind uniform slurry through sand mill and be dried, obtain the not ferric lithium phosphate precursor of carbon coated;
3) by the ferric lithium phosphate precursor of above-mentioned not carbon coated under inert gas shielding atmosphere, carry out first sintering, make notThe LiFePO4 of carbon coated;
4) by the LiFePO4 of the not carbon coated of preparing in step 3) and a certain amount of lithium phosphate, organic carbon source in organic solventCarry out batch mixing for the second time, wherein the interpolation quality of lithium phosphate accounts for not 0～5.5% left and right of the LiFePO4 quality of carbon coated;
5) batch mixing in step 4) is ground in blue-type mulling machine after 2～3 hours, obtain this composite by dry processingPresoma component;
6) will after the presoma component fragmentation of the composite in step 5), under inert gas shielding atmosphere, carry out double sintering;
7) by double sintering material later after 100～300 mesh sieves are processed, finally obtain lithium phosphate/carbon-coated LiFePO 4 for lithium ion batteriesComposite.
Above-mentioned steps 1) described in lithium source be selected from lithium carbonate, lithium hydroxide, lithium acetate, lithium citrate, lithium dihydrogen phosphateOne or more; Described source of iron is selected from the one in iron oxide, tri-iron tetroxide, ironic citrate, ferric phosphate, ferrous oxalateOr multiple; Described phosphorus source is selected from one or more in ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, phosphoric acid, lithium dihydrogen phosphate.
Above-mentioned steps 3) described in first sintering temperature be 400～600 DEG C, the time is 2～10 hours.
Above-mentioned steps 4) described in organic carbon source be selected from glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin,Polyvinyl alcohol, phenolic resins, polyacrylonitrile, starch, cellulosic one or more.
Above-mentioned steps 1) and 4) described in organic solvent be selected from methyl alcohol, ethanol, acetone, METHYLPYRROLIDONE; After batch mixingSolid content is 10～40%.
Above-mentioned steps 1) in through sand mill grind slurry particle diameter control range at 300～500nm.
Above-mentioned steps 2) and 5) described in the dry spray dryer that adopts dry or static dry, wherein preferably spray drying machineInlet temperature is 185 DEG C, and outlet temperature is 100 DEG C, and static being dried at room temperature carried out.
Above-mentioned steps 6) described in for the second time sintering temperature be 650～750 DEG C, the time is 2～10 hours.
Above-mentioned steps 3) and 6) described in inert gas be one or several in argon gas, helium, nitrogen, carbon dioxide.
Above-mentioned steps 7) described in the grain diameter of lithium phosphate/carbon-coated lithium iron phosphate composite at 200～400nm, diameter of particleAt 0.1～50um, carbon content is 1.4～2%.
Beneficial effect of the present invention is:
1) the present invention adopts two-step method to prepare the coated carbon/composite ferric lithium phosphate material of lithium phosphate. Pass through on the one hand a pre-burning,Can reach the controllability of lithium iron phosphate particles size, in two mix, directly add lithium phosphate and carbon source on the other hand, avoid addingEnter miscellaneous that He Lin source, lithium source solid phase reaction generates, thus can real lithium phosphate and carbon source distribute more uniformly on LiFePO4 surface,Finally prepare and there is high conductivity and high performance LiFePO4.
2) provide a kind of lithium phosphate/carbon-coated lithium iron phosphate composite, described lithium phosphate/carbon-coated lithium iron phosphate compositeMore traditional carbon-coated lithium iron phosphate composite has been introduced glassy state fast-ionic conductor ferric phosphate, can effectively improve LiFePO4Electronic conductivity, its conductivity value > 10-3S/cm, lithium ion diffusion coefficient > 1.8 × 10-12cm2/s。
3) provide a kind of lithium phosphate/carbon-coated lithium iron phosphate composite, described lithium phosphate/carbon-coated lithium iron phosphate compositeThe rich composite of more traditional carbon-coated LiFePO 4 for lithium ion batteries contains excessive lithium source, has higher lithium ion conductivity, is improving phosphorusThe chemical property that also can improve LiFePO4 when acid iron lithium electronic conductivity, under its normal temperature, 0.2C electric discharge initial capacity can reach159mAh/g, 1C electric discharge initial capacity can reach 152mAh/g, and 3C electric discharge initial capacity can reach 143mAh/g, and 8C electric discharge just beginsContrary capacity can reach 135mAh/g, and low temperature-20 degree 0.2C discharge capacity can reach 117mAh/g.
Brief description of the drawings
Fig. 1 is the TEM photo of the lithium phosphate/carbon-coated lithium iron phosphate composite prepared according to embodiment 1.
Fig. 2 is the lithium phosphate/carbon-coated lithium iron phosphate composite XRD collection of illustrative plates prepared according to embodiment 1.
Fig. 3 is the chemical property of the lithium phosphate/carbon-coated lithium iron phosphate composite prepared according to embodiment 1.
Detailed description of the invention:
Below by embodiment, the present invention is described in further detail, but this is not limitation of the present invention, those skilled in the artAccording to basic thought of the present invention, can make various amendments or improvement, only otherwise depart from basic thought of the present invention, all at thisWithin scope of invention.
Embodiment 1:
Be that 1:1:1 takes lithium carbonate 111.16g according to lithium, iron, P elements mol ratio, ferrous oxalate 539.41g, ammonium dihydrogen phosphate (ADP)345.36g carry out batch mixing for the first time. Successively ammonium dihydrogen phosphate (ADP), lithium carbonate, ferrous oxalate are joined 3kg is housed every half an hourIn the 10L blue-type mulling machine of ethanol, rotating speed 1500r/min, grinds 2 hours after granularity reaches D50 < 4um, and its slurry is importedIn sand mill, reach after 300-400nm until sand milling granularity, slurry is poured into and in pallet, is placed in ventilating kitchen to carry out static state dry, dryDryly carry out fragmentation after completely. Under nitrogen atmosphere, the material after fragmentation is placed in to tube furnace and carries out first sintering, sintering temperature600 degree, constant temperature 2 hours. Product after 74.14g pre-burning is joined in the 2L blue-type mulling machine of the ethanol that contains 1000ml and carry outBatch mixing for the second time, rotating speed 1000r/min, after grinding half is little, adds lithium phosphate 1.19g, and wherein the addition of lithium phosphate accounts for coated1.6% of LiFePO4 amount, adds sucrose 4.53g again after half an hour, continue to grind, when granularity reaches D50 < 2um discharging, by thisSlurry pours that in pallet, in ventilating kitchen, to carry out static state dry into. After to be dried completing, this material is carried out to fragmentation, and by this fragmentationMaterial under nitrogen environment, be placed in tubular type and carry out double sintering, sintering temperature 700 is spent, constant temperature 10 hours. Treat tube furnace natureAfter cooling, the material of double sintering is carried out to the processing of sieving of 200 orders, obtain lithium phosphate/carbon-coated lithium iron phosphate composite, produceIn thing, carbon content is 1.6%.
The lithium ion cell positive obtaining is carried out to sem observation with lithium phosphate/carbon-coated lithium iron phosphate composite,Result as shown in Figure 1. As seen from Figure 1, lithium phosphate/carbon-coated lithium iron phosphate composite grain diameter size of gained exists250nm left and right, diameter of particle is at 0.1～30um. The XRD collection of illustrative plates showing in Fig. 2 shows, sample spectrogram is mainly ferric phosphateLithium structure phase; Containing a small amount of lithium phosphate (1.56%).
Taking preparation lithium ion cell positive with lithium phosphate/carbon-coated lithium iron phosphate composite as positive electrode, acetylene black for conduct electricityAgent, polytetrafluoroethylene (PTFE) is binding agent, makes electrode slice, taking lithium metal as negative pole, is assembled into simulation button cell. 2～4.0V,Under the different charging and discharging currents conditions of normal temperature, test, the results are shown in accompanying drawing 3. As can be seen from Figure 3, with 34mA/g(0.2C) carry outDischarging and recharging initial reversible capacity is 159.8mAh/g, taking 170mA/g(1C) discharge and recharge initial reversible capacity as152.2mAh/g, taking 340mA/g(2C) discharge and recharge initial reversible capacity as 148.1mAh/g, with 510mA/g(3C)Discharging and recharging initial reversible capacity is 143.8mAh/g, taking 1360mA/g(8C) discharge and recharge initial reversible capacity as135.7mAh/g. Low temperature-20 degree 34mA/g(0.2C) to carry out reversible capability of charging and discharging be 117.7mAh/g.
Experimental example 2
Be that 1:0.9:0.95 takes lithium hydroxide according to lithium, iron, P elements mol ratio, iron oxide, diammonium hydrogen phosphate carries out for the first timeBatch mixing. Successively diammonium hydrogen phosphate, lithium hydroxide, iron oxide are joined to the 10L blue-type mulling that 3kg methyl alcohol is housed every half an hourIn machine, rotating speed 1500r/min, grinds 2 hours after granularity reaches D50 < 4um, and its slurry is imported in sand mill, treats sand millingGranularity reaches after 300-400nm, and slurry is poured into and in pallet, is placed in ventilating kitchen to carry out static state dry, dryly carries out fragmentation after completely.Under helium atmosphere encloses, the material after fragmentation is placed in to tube furnace and carries out first sintering, sintering temperature 500 is spent, constant temperature 2 hours.Product after 71.78g pre-burning is joined in the 2L blue-type mulling machine of the ethanol that contains 1000ml and carry out batch mixing for the second time, rotating speed1000r/min, grind half little after, add part lithium phosphate 1.79g, wherein the addition of lithium phosphate accounts for coated LiFePO 4 for lithium ion batteries amount not2.5%, after half an hour, add glucose 4.57g, continue to grind, when granularity reaches D50 < 2um discharging, pour this slurry into palletIn in ventilating kitchen, be dried. After to be dried completing, this material is carried out to fragmentation, and by this broken material in helium environmentUnder be placed in tube furnace and carry out double sintering, sintering temperature 750 is spent, constant temperature 2 hours. After tube furnace is lowered the temperature naturally, by secondaryThe material of sintering carries out the processing of sieving of 200 orders, obtains lithium phosphate/carbon-coated lithium iron phosphate composite, and in product, carbon content is 1.7%,Its grain diameter is in 300nm left and right, and diameter of particle is in 1～45um left and right.
Taking preparation lithium ion cell positive with lithium phosphate/carbon-coated lithium iron phosphate composite as positive electrode, acetylene black for conduct electricityAgent, polytetrafluoroethylene (PTFE) is binding agent, makes electrode slice, taking lithium metal as negative pole, is assembled into simulation button cell. 2～4.0V,Under the different charging and discharging currents conditions of normal temperature, test, taking 34mA/g(0.2C) discharge and recharge initial reversible capacity as 155.6mAh/g,Taking 170mA/g(1C) discharge and recharge initial reversible capacity as 147mAh/g, low temperature-20 degree 34mA/g(0.2C) carry outReversible capability of charging and discharging is 108.9mAh/g.
Experimental example 3
Be that 1:0.97:0.98 takes lithium acetate according to lithium, iron, P elements mol ratio, ironic citrate, phosphoric acid carries out batch mixing for the first time.Successively phosphoric acid, lithium acetate, ironic citrate are joined in the 10L blue-type mulling machine that 3kg acetone is housed to rotating speed every half an hour1500r/min, grinds 2 hours after granularity reaches D50 < 4um, and its slurry is imported in sand mill, treats that sand milling granularity reachesAfter 300-400nm, slurry is poured into and in pallet, is placed in ventilating kitchen and is dried, dryly carry out fragmentation after completely. Under argon atmosphere,Material after fragmentation is placed in to tube furnace and carries out first sintering, sintering temperature 400 is spent, constant temperature 10 hours. By 69.41g pre-burningAfter product join in the 2L blue-type mulling machine that contains 1000mlN-N-methyl-2-2-pyrrolidone N-and carry out batch mixing for the second time, rotating speed1000r/min, grind half little after, calculate according to conservation of matter principle, add part lithium phosphate 2.31g, wherein lithium phosphateAddition accounts for 3.3% of coated LiFePO 4 for lithium ion batteries amount not, adds citric acid 4.20g after half an hour, continues to grind, when granularity reachesD50 < 2um discharging, pours this slurry in pallet into and is dried in ventilating kitchen. After to be dried completing, this material is brokenBroken, and this broken material is placed in to tube furnace under ar gas environment carries out double sintering, sintering temperature 650 is spent, constant temperature 10Hour. After tube furnace is lowered the temperature naturally, the material of double sintering is carried out to the processing of sieving of 200 orders, obtain the coated phosphorus of lithium phosphate/carbonAcid iron lithium composite material, in product, carbon content is 1.4%, and its grain diameter is in 320nm left and right, and diameter of particle is on 1.5～45um left sideRight.
Experimental example 4
Be that 1.09:1:1.03 takes lithium citrate according to lithium, iron, P elements mol ratio, tri-iron tetroxide, lithium dihydrogen phosphate carries outBatch mixing for the first time. Successively lithium dihydrogen phosphate, lithium citrate, tri-iron tetroxide are joined 4kg deionized water is housed every half an hour10L blue-type mulling machine in, rotating speed 1500r/min, grinds 2 hours after granularity reaches D50 < 4um, and its slurry is imported to sand millingIn machine, reach after 300-400nm until sand milling granularity, slow slurry injection is placed in to spray dryer and is dried, completely dryAfter carry out fragmentation. Under carbon dioxide atmosphere, the material after fragmentation is placed in to tube furnace and carries out first sintering, sintering temperature 600Degree, constant temperature 3 hours. Product after 64.48g pre-burning is joined in the 2L blue-type mulling machine of the methyl alcohol that contains 1000ml and carry out secondInferior batch mixing, rotating speed 1000r/min, after grinding half is little, calculates according to conservation of matter principle, adds part lithium phosphate 3.47g;Wherein the addition of lithium phosphate accounts for 5.3% of coated LiFePO 4 for lithium ion batteries amount not, adds phenolic resins 2.05g after half an hour, continue to grind,When granularity reaches D50 < 2um discharging, this slurry is poured in pallet and is dried in ventilating kitchen. After to be dried completing, by thisMaterial carries out fragmentation, and this broken material is placed in to tube furnace under nitrogen environment carries out double sintering, sintering temperature 700Degree, constant temperature 9 hours. After tube furnace is lowered the temperature naturally, the material of double sintering is carried out to the processing of sieving of 200 orders, obtain lithium phosphate/Carbon-coated lithium iron phosphate composite, in product, carbon content is 2.0%, and its grain diameter is in 400nm left and right, and diameter of particle exists2.5～50um left and right.
Experimental example 5
Be that 1.06:1:1.02 takes lithium carbonate according to lithium, iron, P elements mol ratio, ironic citrate, ammonium dihydrogen phosphate (ADP) carries out firstInferior batch mixing. Successively ammonium dihydrogen phosphate (ADP), lithium carbonate, ironic citrate are joined 3.5kgN-methyl-2-pyrrolidines is housed every half an hourIn the 10L blue-type mulling machine of ketone, rotating speed 1500r/min, grinds 3 hours after granularity reaches D50 < 4um, and its slurry is imported to sandIn grinding machine, reach after 300-400nm until sand milling granularity, slurry is poured into and in pallet, is placed in ventilating kitchen and is dried, completely dryAfter carry out fragmentation. Under nitrogen atmosphere, the material after fragmentation is placed in to tube furnace and carries out first sintering, sintering temperature 550 is spent,Constant temperature 7 hours. Product after 76.51g pre-burning is joined in the 2L blue-type mulling machine of the acetone that contains 1000ml and mix for the second timeMaterial, rotating speed 1000r/min, after grinding half is little, calculates according to conservation of matter principle, adds part lithium phosphate 0.596g, itsThe addition of middle lithium phosphate accounts for 0.77% of coated LiFePO 4 for lithium ion batteries amount not, adds polyacrylonitrile 15.31g after half an hour, continue to grind,When granularity reaches D50 < 2um discharging, this slurry is poured in pallet and is dried in ventilating kitchen. After to be dried completing, by thisMaterial carries out fragmentation, and this broken material is placed in to tube furnace under nitrogen environment carries out double sintering, sintering temperature 700Degree, constant temperature 5 hours. After tube furnace is lowered the temperature naturally, the material of double sintering is carried out to the processing of sieving of 200 orders, obtain lithium phosphate/Carbon-coated lithium iron phosphate composite, in product, carbon content is 1.6%. Its grain diameter is in 200nm left and right, and diameter of particle exists0.2～25um left and right.
Claims (10)
1. a preparation method for lithium phosphate/carbon-coated lithium iron phosphate composite, concrete steps are as follows:
1) be 1～1.2:0.9～1.2:0.9～1.2 by lithium source, source of iron, phosphorus source by element mol ratio, organic solvent or go fromIn sub-water, carry out batch mixing for the first time, phosphorus source, lithium source, source of iron are joined in blue-type mulling machine sequentially, grind 2～3After hour, the slurry grinding out is poured in sand mill and is ground;
2) will grind uniform slurry through sand mill and be dried, obtain the not ferric lithium phosphate precursor of carbon coated;
3) by above-mentioned ferric lithium phosphate precursor under inert gas shielding atmosphere, carry out first sintering, obtain carbon coated notLiFePO4;
4) by step 3) in the LiFePO4 of not carbon coated of preparation join in the blue-type mulling machine that contains organic solvent and carry outBatch mixing for the second time, adds lithium phosphate after grinding, wherein the addition of lithium phosphate accounts for 0～5.5% of carbon coated LiFePO4 amount not,Then add organic carbon source, continue to grind;
5) by step 4) in batch mixing in blue-type mulling machine, grind after 2～3 hours, obtain this composite wood by dry processingThe presoma component of material;
6) by step 5) in the presoma component fragmentation of composite after under inert gas shielding atmosphere, carry out double sintering;
7) by double sintering material later after 100～300 mesh sieves are processed, final that lithium phosphate/carbon-coated LiFePO 4 for lithium ion batteries is multipleCondensation material.
2. preparation method as claimed in claim 1, is characterized in that step 1) described in lithium source be selected from lithium carbonate, hydrogen-oxygenOne or more in change lithium, lithium acetate, lithium citrate, lithium dihydrogen phosphate; Described source of iron is selected from iron oxide, four oxidationsOne or more in three-iron, ironic citrate, ferric phosphate, ferrous oxalate; Described phosphorus source is selected from ammonium dihydrogen phosphate (ADP), phosphoric acidOne or more in hydrogen two ammoniums, phosphoric acid, lithium dihydrogen phosphate.
3. preparation method as claimed in claim 1, is characterized in that step 3) described in first sintering temperature be 400～600DEG C, the time is 2～10 hours.
4. preparation method as claimed in claim 1, is characterized in that step 4) described in organic carbon source be selected from glucose,Sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, polyvinyl alcohol, phenolic resins, polyacrylonitrile, starch, fibreOne or more of dimension element.
5. preparation method as claimed in claim 1, is characterized in that step 1) and 4) described in organic solvent be selected from methyl alcohol,Ethanol, acetone, METHYLPYRROLIDONE.
6. preparation method as claimed in claim 1, is characterized in that, the slurry particle diameter control range of grinding through sand mill exists300～500nm。
7. preparation method as claimed in claim 1, is characterized in that step 2) and 5) described in be dried as spray dryerDry or static dry.
8. preparation method as claimed in claim 1, is characterized in that step 6) described in for the second time sintering temperature be 650～750DEG C, the time is 2～10 hours.
9. preparation method as claimed in claim 1, is characterized in that step 3) and 6) described in inert gas be argon gas,One or several in helium, nitrogen, carbon dioxide.
10. preparation method as claimed in claim 1, is characterized in that step 7) described in lithium phosphate/carbon-coated LiFePO 4 for lithium ion batteries multipleThe grain diameter of condensation material is at 200～400nm, and diameter of particle is at 0.1～50um, and carbon content is 1.4～2%.
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